9,10-dihydro-9,10-dioxoanthracenediyl- bis-(4&#39;-carbamoylphthalimides



United States Patent 3,483,217 9,10-DlHYDRO-9,10-DIOXOANTHRACENEDIYL-BIS-(4-CARBAMOYLPHTHALIMIDES John F. Santimauro, Wyckolf, NJ., andHerman Gerson,

New York, N.Y., assignors to Allied Chemical Corporation, New York,N.Y., a corporation of New York No Drawing. Filed Dec. 2, 1966, Ser. No.598,632 Int. Cl. C09b 1/46 US. Cl. 260326 5 Claims ABSTRACT OF THEDISCLOSURE Production of diimides obtained by reaction of a dianhydride,derived from trimellitic acid and a diamino anthraquinone, and a primaryorganic amine. The resultant diimides exhibit utility as colorants, i.e.pigments, for organic polymeric masses which are characterized byexcellent non-bleeding and light-fastness properties as well asbrightness and clarity of shade.

lowing general formula:

N H N R O m (a), (R l o c 2 wherein:

R is the residue of a primary organic amine such as an aliphatic oraromatic radical, or heterocyclic radical whose hetero ring member isnitrogen or nitrogen in combination with sulfur, oxygen, or nitrogen,said aliphatic, aromatic or heterocyclic radical being substituted orunsubstituted and containing 1 to 18 carbon atoms; R R and Rindependently represent hydrogen, halogen, nitro, trifiuoromethyl,alkyl, alkoxy dialkylamino, and dialkylsulfamyl radicals, wherein theaforementioned alkyl moeities contain from 1 to 6 carbon atoms; and a,b, and 0 independently represent integers from 1 to 3.

We have found the novel compounds of the present invention to be usefuland valuable pigments. After being processed into a finely divided form,they may be used for coloring organic polymeric materials (such asvarnishes and plastics), for the manufacture of printing colors and forspin-dyeing of synthetic fibers such as viscose rayon, nylon 6, nylon 6,6, or polyester fiber. In all of these applications, the novel colorantsmay be incorporated into the organic products bymethods conventional tothese several arts. The products of this in- Patented Dec. 9, 1969 vofiK/piio 6 l m M. zl.

and a primary organic amine, preferably in excess, said amine having thefollowing formula:

wherein R, R R R a, b, and c have the same significance as describedabove. The anhydride component of the above reaction forms the subjectof our copending application No. 598,592, now US. Patent No. 3,390,155,entitled Novel Dianhydrides and filed of even date. The reaction isperformed preferably in the presence of an inert solvent, e.g.,N,N-dirnethylacetamide, nitroben- Zene, xylene, toluene, and the like,and mixtures thereof. Water formed as a by-product during the course ofthe reaction can be removed by azeotropic distillation with the solvent.Temperatures above C., preferably within the range of about to C., areused. The time required will vary inversely with the temperature, but ingeneral from about 5 to about 48 hours will sufiice to enable thereaction to proceed essentially to completion. The product, a bis-imide,is generally insoluble in the reaction mixture and can be separatedtherefrom by filtration or any other convenient means. The product canthen be purified by washing with solvents and/0r reslurrying in diluteaqueous acid (to remove unreacted amine) or in dilute aqueous alkali (toremove unreacted anhydride or acidic by-products). The conversion of theresultant purified product to colorant form can be accomplished byconventional means, e.g., grinding with salt, sand, pebbles, vatting,acid pasting, and the like.

The following list of amines which can be used in the above reaction isprovided by way of illustration and is not meant to include all thevariations falling within the scope of and contemplated as part of ourinvention. Aliphatic primary amines:

methylamine n-propylamine n-butylamine 1-amino-2-ethylhexanen-decylamine cyclohexylamine Z-aminoethanol l-aminoindane laurylaminestearylamine 2-methoxyethylamine benzylamine Aromatic primary amines: J

aniline the o,-m,p-toluidines the o,m,p-xylidines hydride in about 420parts of anhydrous nitrobenzene was heated to and maintained at about125 for 18 hours. The reaction mixture was cooled to room temperature,the resultant slurry filtered andthe filter cake Washed with alcohol.The washed cake of 9,10-dihydro-9,10-dloxanthracene 1,5 diyl bis (4carbamoylphthalic anhydride) was dried in air.

B. Preparation of a bis-imide A mixture of 20 parts of the dianhydrideprepared as described in part A above, 9.4 parts of p-anisidine (10%excess) and about 200 parts .by volume of N,N-dimethylacetamide washeated to 145 over a period of 2% hours and maintained at 145 to 150 for18 hours. The resulting product slurry was filtered and washed firstwith xylene and then with alcohol. The washed cake was reslurried inabout 500 parts of Water containing 15 parts of sodium carbonate. Theslurry was agitated for about 4 hours and then filtered. The yellowsolid was washed with water and dried in a circulating air oven. The dryproduct was obtained in a yield of about 91% of theory and has thefollowing formula:

9,IO-DIHYDRO-Q,10-DIOXOANTHRACENE 1,5 DIYL-BIS- 4CARBAMOYL-N-(4-METHOXYPHENYL)-PHTHAL- IMIDE) The following examples willfurther illustrate the products and process of the present invention.The temperatures are given in degrees centigrade, and parts andpercentages are by weight unless otherwise specified.

EXAMPLE 1 A. Preparation of a dianhydride A mixture of 27.5 parts of1,5-diaminoanthraquinone and 48.4 parts of trimellitic 4-monoacidchloride, 1,2-an- It neither melts nor decomposes at temperatures below320". The new compound is soluble in alkaline hydrosulfate from which itcan be recovered unchanged by oxidation in accordance with theconventional vatting procedures.

Analysis.Calcd. for C H O N C, 69.3; H, 3.5; N, 7.2; O, 21.0. Found: C,68.2; H, 3.6; N, 7.2; O, 21.0.

When reduced to fine pigment form and incorporated into acrylic lacquersin the conventional manner, the product of this example gives excellentnon-bleeding, lightfast colorations which are bright yellow.

EXAMPLE 2 The procedure of Example 1, part B, was repeated using anequivalent amount of m-chloro-p-methoxyaniline in place of p-anisidine.The product, 9,10-dihydro-9,10-dioxoanthracene 1,5 diyl bis (4'carbamoyl N(3"- chloro-4"-methoxyphenyl)phthalimide), was obtained inexcellent yield as a yellow granular solid.

EXAMPLE 3 The procedure described in Example 1, part B, was repeatedexcept that an equivalent amount of p-phenoxyaniline was used in placeof p-anisidine.

The product, 9,10-dihydro 9,10 dioxoanthracene-1,5- diyl bis (4'carbamoyl N (4" phenoxyphenyl) phthalimide), was obtained as a yellowsolid in excellent yield.

EXAMPLE 4 The procedure of Example 1, part A, was repeated using1,4diaminoanthraquinone in place of 1,5-diaminoanthraquinone. Theresulting dianhydride product was reacted with p-anisidine exactly asdescribed in part B of Example 1 to yield a reddish brown solid,9,10-dihydro- 5 6 9,10 dioxoanthracene 1,4 diyl bis (4' carbamoyl- Weclaim: N-(4-methoxyphenyl)phthalimide), in good yield. 1. A compoundhaving the following formula:

EXAMPLE 5 The procedure of Example 1 was repeated using, 1,8- i mitt!diaminoanthraquinone in place of 1,5-diaminoanthraquinone and aniline inplace of the p-anisidine, both being (R used in essentially equivalentamounts as indicated in (R (a 0 2 Example 1. The resultant product,9,l0-dihydro-9,l0-di- 2 b oxoanthracene 1,8 diyl his (4' carbamoyl N whre n phenylphthalimide) was obtained in good yield. This prod- R is aphenoxyor an alkoxy-substituted phenyl whereuct was purified bydissolving in hot aqueous sodium in said alkoxy substituent containsfrom 1 to 5 carhydrosulfite. The solution was filtered and the clarifiedbon atoms; R R and R independently represent filtrate was oxidized bythe addition of aqueous sodium members selected from the groupconsisting of hydichromate. The precipitated product was filtered anddrogen, halogen, nitro, trifiuorornethyl, alkyl, alkoxy, washed wellwith hot water. The product was shown to dialkylamino, anddialkylsulfamyl radicals, Whreifl have excellent mass color whenevaluated according to the alkyl moieties 011 Said radicals contain from1 ASTM D-387-60 Procedure B. to 6 carbon atoms; and a, b, and 0independently It can thus be seen that a novel class of bis-imidecomrepr sent members selected from the group of inteponnds has beenprovided which are useful as colorants gers consisting of 2, and fororganic polymeric products. 2. A compound according to claim 1 havingthe fol- The present invention has been described and illustrated lowingformula:

0 HN t I ll 0 o I r NH 0 l by means of several examples which, althoughthey dis- 3. A compound according to claim 1 having the folclose thebest manner known to us of carrying out the lowing formula:

process of our invention, are to be considered as descrip- 4. A compoundaccording to claim 1 having the foltive rather than limitative. lowingformula:

7 5. A compound according to claim 1 having the following forrnulaz HOCH;

8 Refgl en ces Cited 3,126,595 3/1964 Kitahbnoki t a1. 260 326 3,312,7154/1967 Anderson 6t :11. 260-326 3,356,672 12/1967 Schefczik 260-152 ALEXMAZEL,. Primary Examiner I; A. NARCAVAG'E, Assistant Examiner 7 US. Cl.X.R.

